CN110232983B - Thick film resistor slurry for ceramic piezoresistive pressure sensor and preparation method thereof - Google Patents
Thick film resistor slurry for ceramic piezoresistive pressure sensor and preparation method thereof Download PDFInfo
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
- H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
- H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
- H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
- H01C17/0652—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component containing carbon or carbides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
- H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
- H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
- H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
- H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
- H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
- H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
- H01C17/06573—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder
- H01C17/0658—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder composed of inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
- H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
- H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
- H01C17/06573—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder
- H01C17/06586—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder composed of organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/003—Thick film resistors
Abstract
A thick film resistance paste for a ceramic piezoresistive pressure sensor and a preparation method thereof relate to the field of thick film electronic materials, and comprise conductive phases: the components are ruthenium oxide and ruthenium oxide/carbon nano tube composite material; inorganic binder phase: the component is CaO, B2O3，SiO2And ZrO2(ii) a Organic carrier: the components are organic solvent, thickener, surfactant, thixotropic agent and rheological agent; and a modifier: the components are polyacrylic resin coated silicon dioxide and lead oxide, the ruthenium oxide/carbon nano tube composite material is added into the conductive phase of the thick film resistor paste, so that the conductive performance of the conductive phase is improved, and the thick film resistor paste has high stability.
Description
Technical Field
The invention relates to the field of thick film electronic materials, in particular to thick film resistor paste for a ceramic piezoresistive pressure sensor and a preparation method thereof.
Background
The sensor technology is one of the high and new technologies which are developed rapidly and is also an important mark for the development of modern science and technology. As an antenna for human to detect external information, the sensor technology is a technology for acquiring information in various forms with high precision, high efficiency and high reliability, converts non-electric quantity information into electric quantity information which is easy to process, creates necessary conditions for people to further know and reform the world, and provides a new method. At present, pressure sensors play an important role in automatic control and detection, pressure plays an important role in the detection of measurement and control systems of modern automation equipment, and the higher the automation degree of the measurement and control systems, the more pressure is monitored, the more demand is placed on the pressure sensors, and therefore, the quality of the sensors determines the performance of the measurement and control systems to a certain extent. The pressure sensor is used for sensing a pressure signal and converting the pressure signal into an available output electric signal according to a certain rule, is mainly used for direct measurement of forces such as tension and pressure and conversion of physical quantities such as liquid level and acceleration, and is one of sensors with the largest demand and the widest application range in agricultural and industrial production, so that the pressure sensor is the sensor with the largest demand. The thick film pressure sensor has been widely used in various fields of various industries, especially in the air conditioner and automobile field, after decades of researches on related technologies of sensors by researchers. However, the prior art also has the problems of large resistance value, low strain coefficient, poor stability and the like of the resistor paste used for the thick film pressure sensor, so that the full-scale output of the thick film pressure sensor is low, and the strain sensitivity is correspondingly low.
For example, a method for preparing a thick film resistor paste disclosed in chinese patent document, whose publication No. CN108091413A, discloses a method for preparing a thick film resistor paste, comprising the steps of: (1) mixing ruthenium powder, titanium diboride, lanthanum oxide, superfine palladium powder, bismuth subcarbonate, barium bismuthate and cobaltous oxide, and placing the mixture into a ball milling tank for ball milling; (2) carrying out suction filtration, drying and sintering in a resistance furnace; (3) cooling to room temperature, and placing the mixture into an agate ball mill for ball milling to obtain a functional phase A; (4) mixing terpineol, polyvinylpyrrolidone, polyanionic cellulose and phenolated enzymatic hydrolysis lignin, heating in water bath at 90-95 deg.C under stirring, adding sodium glycocholate, lauric acid, ethylene glycol, Turkey red oil and palm oil, and stirring; (5) and adding the functional phase A and the glass powder, and rolling on a three-roll mill to obtain the thick film resistor paste, wherein the thick film resistor paste prepared by the method has larger resistance and poorer stability.
Disclosure of Invention
The invention provides thick-film resistor paste for a ceramic piezoresistive pressure sensor and a preparation method thereof, aiming at overcoming the problems of larger resistance value, lower strain coefficient, poorer stability and the like of the resistor paste for the thick-film pressure sensor in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a thick film resistor paste for a ceramic piezoresistive pressure sensor, comprising a conductive phase: the components and the parts by mass are 50-60 parts of ruthenium oxide and 5-10 parts of ruthenium oxide/carbon nano tube composite material; inorganic binder phase: the components and the parts by mass are that CaO40-50 parts and B2O340-50 parts of SiO245-55 parts and ZrO215-20 parts of a solvent; organic carrier: the components and the parts by mass are 90-95 parts of organic solvent, 2-5 parts of thickening agent, 0.5-1 part of surfactant, 1-2 parts of thixotropic agent and 0.5-1 part of rheological agent; and a modifier: the components and the parts by mass are 70-90 parts of polyacrylic resin coated silicon dioxide and 30-40 parts of lead oxide.
In the invention, the conductive phase consists of ruthenium oxide and ruthenium oxide/carbon nanotube composite material, the ruthenium oxide/carbon nanotube composite material is characterized in that ruthenium oxide is loaded on the carbon nanotube, so that the surface area is larger, the conductivity of ruthenium oxide is further improved, and compared with the prior art that a carbon-based conductive filler is directly added in ruthenium oxide, and the like, partial ruthenium oxide is loaded on the carbon nanotube firstly and then mixed with ruthenium oxide powder, so that the phenomenon that the carbon-based conductive filler is agglomerated during mixing can be prevented, and the thick film resistor slurry is unstable in performance and easy to fluctuate during use after being printed and fired.
The inorganic binding phase adopts CaO and B2O3、SiO2And ZrO2Is prepared from ZrO2In the silicate glass system, the solubility is small, the viscosity of the inorganic binder phase can be remarkably improved, the thermal expansion coefficient can be properly reduced, and B2O3The glass has the effect of reducing the thermal expansion coefficient of the glass and the surface tension of the glass, and can improve the chemical stability of the glass.
In the organic carrier, the surface active agent can reduce the surface tension between the organic carrier and the solid particles, so that the organic carrier can fully wet the solid particles, the tendency of mutual agglomeration among the particles is reduced, the stability is improved, and the leveling agent can enable the thick film resistance paste to be leveled in a very short time after the printing is finished, so that a continuous film is formed, the trace of a silk screen is eliminated, and the material stability is improved.
The invention also adds a modifier, the doping of the modifier can change the temperature coefficient, the strain coefficient and the like of the resistance paste, wherein the modifier consists of polyacrylic resin coated silicon dioxide and lead oxide, wherein the polyacrylic resin coated silicon dioxide does not react with a conductive phase, the polyacrylic resin coated silicon dioxide has higher diffusion coefficient, a thicker transition layer is easy to form between the thick film strain resistance film layer and the ceramic substrate after doping and sintering, the interface bonding force of the resistance film layer and the substrate is improved by the transition layer, the strain coefficient is improved, and compared with the resistance paste, the invention has the advantages that the temperature coefficient, the strain coefficient and the like of the resistance paste can be changed by doping the modifierThe surface of the silica which is not coated and is coated by the polyacrylic resin has a polymer layer, so that the dispersibility of the silica in a solvent is improved, and the phenomenon of agglomeration is prevented, so that the resistance performance of a thick film is unstable; and when the resistance paste is sintered, the polyacrylic resin coated outside the silicon dioxide can soften and flow after the organic carrier is completely volatilized, the conductive phase is coated, and the conductive phase can be bonded and fixed on the substrate after the temperature is reduced, so that the adhesion force of the resistance film layer and the substrate is further increased. Lead oxide in the modifier can react with ruthenium dioxide to generate ruthenate Pb2Ru2O6.5The conductive phase is used for alleviating the phenomenon that the sheet resistance is suddenly increased due to the fact that the polyacrylic resin coats the silicon dioxide.
Preferably, the organic solvent is one or a combination of diethylene glycol monomethyl ether, tributyl citrate, tributyl phosphate, terpineol and butyl carbitol, the thickener is one of ethyl cellulose, hydroxyethyl cellulose and carboxymethyl cellulose, the surfactant is lecithin, the thixotropic agent is one or a combination of cetyl alcohol, polyamide wax and castor oil, and the rheological agent is 1, 4-butyrolactone.
A preparation method of thick film resistor slurry for a ceramic piezoresistive pressure sensor is characterized by comprising the following preparation steps:
s1: preparing a conductive phase:
s1.1: adding deionized water into ruthenium trichloride to prepare a ruthenium trichloride solution of 0.1-0.15mol/L, then adding a carbon nano tube, heating to 60-70 ℃, stirring, then dropwise adding a sodium hydroxide solution, continuously stirring and aging for 2-4h, then centrifugally washing, and calcining to obtain a ruthenium oxide/carbon nano tube composite material;
s1.2: mixing ruthenium oxide powder and a ruthenium oxide/carbon nano tube composite material to prepare a conductive phase;
s2: preparation of inorganic binder phase: CaO, B2O3、SiO2And ZrO2Adding the mixture into an agate ball-milling tank according to the proportion, stirring for 1-2h, then placing the mixture into a crucible, smelting for 1.5-2h at the temperature of 1100-1300 ℃, performing water quenching, and then performing ball milling for 10-15h to prepare the materialObtaining an inorganic binder phase;
s3: preparation of organic vehicle: mixing an organic solvent and a thickening agent in a water bath at 70-85 ℃, stirring until the thickening agent is completely dissolved in the organic solvent, then adding a surfactant, a thixotropic agent and a rheological agent, and uniformly stirring to obtain an organic carrier;
s4: preparing a modifier:
s4.1: placing the silicon dioxide particles in absolute ethyl alcohol, adding 3-aminopropyltriethoxysilane, reacting for 7-14h at 30-50 ℃, and centrifugally drying to obtain amino modified silicon dioxide particles; dispersing amino modified silica particles into toluene, adding triethylamine, stirring for 1-2h at 0 ℃ under the protection of nitrogen, adding 2-bromine isobutyryl bromide, stirring for reaction for 10-15h, and centrifugally drying to obtain bromine modified silica particles; then, dispersing bromine-modified silica particles, ferric trichloride hexahydrate and triphenylphosphine in N, N-dimethylformamide, replacing by argon, adding ethyl 2-bromoisobutyrate and methyl methacrylate, stirring and mixing, slowly adding ascorbic acid, reacting at 50-80 ℃ for 20-28h, centrifuging, washing and drying to obtain polyacrylic resin coated silica;
s4.2: mixing polyacrylic resin coated silicon dioxide and lead oxide to obtain a modifier;
s5: and mixing and grinding the conductive phase and the inorganic bonding phase, then placing the mixture in an organic carrier, and adding a modifier to obtain the thick-film resistor paste for the ceramic piezoresistive pressure sensor.
When the polyacrylic resin coated silica is prepared, firstly, silica and 3-aminopropyltriethoxysilane are reacted, amino is introduced on the silica to obtain amino modified silica particles, then, the amino on the silica is reacted with 2-bromoisobutyryl bromide to obtain bromine modified silica particles, and finally, monomer methyl methacrylate is grafted on the surface of the silica particles to obtain the polyacrylic resin coated silica.
Preferably, in step S1.1, the mass ratio of ruthenium trichloride to carbon nanotubes is: 1-3:1.
Preferably, the calcination in step S1.1 is carried out at a temperature of 250-350 ℃ for a period of 15-24 h.
Preferably, the mass ratio of the ferric chloride hexahydrate and the triphenylphosphine in the step S4.1 is 1: 10-15.
Preferably, the mass ratio of the bromine-modified silica particles to the methyl methacrylate in step S4.1 is 1: 100-150.
Preferably, the particle size of the polyacrylic resin coated silicon dioxide and lead oxide in the step S4.2 is 1-3 μm.
Therefore, the invention has the following beneficial effects: the ruthenium oxide/carbon nano tube composite material is added into the conductive phase of the thick film resistor paste, so that the conductive performance of the conductive phase is improved, the stability is high, and the polyacrylic resin coated silicon dioxide and lead oxide mixed modifier is added into the thick film resistor paste, so that the strain coefficient of the thick film resistor paste after sintering is improved, the resistance value is reduced, and the performance stability and the adhesion with a substrate are improved.
Detailed Description
The invention is further described with reference to specific embodiments.
Example 1: a preparation method of thick film resistor slurry for a ceramic piezoresistive pressure sensor comprises the following preparation steps:
s1: preparing a conductive phase:
s1.1: adding deionized water into 1.5g of ruthenium trichloride to prepare a 0.1mol/L ruthenium trichloride solution, then adding 1.5g of carbon nano tube, heating to 60 ℃, stirring, then dropwise adding a sodium hydroxide solution, continuously stirring and aging for 2 hours, then centrifugally washing, and calcining at 300 ℃ for 20 hours to obtain a ruthenium oxide/carbon nano tube composite material;
s1.2: mixing 28.8g of ruthenium oxide powder and 2.4g of ruthenium oxide/carbon nanotube composite material to prepare a conductive phase;
s2: preparation of inorganic binder phase: CaO, B2O3、SiO2And ZrO2Adding the mixture into an agate ball-milling tank according to the proportion of 5:4.5:5.5:1.5, stirring for 1h, then placing the mixture into a crucible, smelting for 2h at 1100 ℃, performing water quenching, then performing ball milling for 10h,preparing an inorganic binding phase;
s3: preparation of organic vehicle: mixing tributyl citrate, butyl carbitol, tributyl phosphate and carboxymethyl cellulose in a water bath at the temperature of 80 ℃, stirring until the carboxymethyl cellulose is completely dissolved in a mixed solvent of the tributyl citrate, the butyl carbitol and the tributyl phosphate, then adding lecithin, castor oil and 1, 4-butyrolactone, and uniformly stirring to obtain an organic carrier, wherein the mass ratio of the tributyl citrate, the butyl carbitol, the tributyl phosphate, the carboxymethyl cellulose, the lecithin, the castor oil and the 1, 4-butyrolactone is 35:30:30:3:1:1: 0.7;
s4: preparing a modifier:
s4.1: placing 0.58g of silicon dioxide particles into absolute ethyl alcohol, adding 0.15mL of 3-aminopropyltriethoxysilane, reacting for 10h at 40 ℃, and centrifugally drying to obtain amino modified silicon dioxide particles; dispersing the amino modified silica particles into 30mL of toluene, adding 1.5mL of triethylamine, stirring at 0 ℃ for 1.5h under the protection of nitrogen, adding 2-bromoisobutyryl bromide, stirring for reacting for 13h, and centrifugally drying to obtain bromine modified silica particles; subsequently, 0.52g of bromine-modified silica particles, 0.043g of ferric trichloride hexahydrate and 0.3g of triphenylphosphine were dispersed in 90ml of N, N-dimethylformamide, and after replacement by argon gas, 0.15g of 2-ethyl bromoisobutyrate and 78g of methyl methacrylate were added, and mixed with stirring, 0.21g of ascorbic acid was slowly added, reacted at 70 ℃ for 24 hours, washed and dried by centrifugation, to obtain a polyacrylic resin-coated silica;
s4.2: mixing polyacrylic resin coated silicon dioxide and lead oxide to obtain a modifier, wherein 90 parts of polyacrylic resin coated silicon dioxide and 40 parts of lead oxide are mixed;
s5: mixing and grinding the conductive phase and the inorganic bonding phase, then placing the mixture in an organic carrier, and adding a modifier to obtain the thick film resistor paste for the ceramic piezoresistive pressure sensor, wherein the mass ratio of the conductive phase to the inorganic bonding phase to the organic carrier to the modifier is as follows: 35:25:25:3.
Example 2: a preparation method of thick film resistor slurry for a ceramic piezoresistive pressure sensor comprises the following preparation steps:
s1: preparing a conductive phase:
s1.1: adding deionized water into 3.1g of ruthenium trichloride to prepare a 0.13mol/L ruthenium trichloride solution, then adding 1.45g of carbon nano tube, heating to 65 ℃, stirring, then dropwise adding a sodium hydroxide solution, continuously stirring and aging for 3 hours, then centrifugally washing, and calcining for 24 hours at 250 ℃ to obtain a ruthenium oxide/carbon nano tube composite material;
s1.2: mixing 26.7g of ruthenium oxide powder and 3.8g of ruthenium oxide/carbon nanotube composite material to prepare a conductive phase;
s2: preparation of inorganic binder phase: CaO, B2O3、SiO2And ZrO2Adding the mixture into an agate ball-milling tank according to the ratio of 4:5:5:2, stirring for 2h, then placing the mixture into a crucible, smelting for 1.5h at 1300 ℃, performing water quenching, and then performing ball milling for 15h to prepare an inorganic bonding phase;
s3: preparation of organic vehicle: mixing terpineol and hydroxyethyl cellulose in a water bath at 85 ℃, stirring until the hydroxyethyl cellulose is completely dissolved in the terpineol, then adding lecithin, polyamide wax and 1, 4-butyrolactone, and uniformly stirring to obtain an organic carrier, wherein the mass ratio of the terpineol, the hydroxyethyl cellulose, the lecithin, the polyamide wax and the 1, 4-butyrolactone is 90:5:0.7:2: 0.5;
s4: preparing a modifier:
s4.1: putting 0.51g of silicon dioxide particles into 25mL of absolute ethyl alcohol, adding 0.12mL of 3-aminopropyltriethoxysilane, reacting for 14h at 30 ℃, and centrifugally drying to obtain amino modified silicon dioxide particles; dispersing amino modified silica particles into 25mL of toluene, adding 1.5mL of triethylamine, stirring for 2h at 0 ℃ under the protection of nitrogen, adding 2.1mL of 2-bromine isobutyryl bromide, stirring for reaction for 10h, and centrifugally drying to obtain bromine modified silica particles; subsequently, 0.47g of bromine-modified silica particles, 0.038g of ferric trichloride hexahydrate and 0.19g of triphenylphosphine were dispersed in 60mL of N, N-dimethylformamide, and after replacement by argon, 0.13g of 2-ethyl bromoisobutyrate and 61.1g of methyl methacrylate were added, mixed with stirring, 0.18g of ascorbic acid was slowly added, reacted at 50 ℃ for 28 hours, centrifugally washed and dried to obtain polyacrylic resin-coated silica;
s4.2: mixing polyacrylic resin coated silicon dioxide and lead oxide to obtain a modifier, wherein 80 parts of polyacrylic resin coated silicon dioxide and 30 parts of lead oxide are mixed;
s5: mixing and grinding the conductive phase and the inorganic bonding phase, then placing the mixture in an organic carrier, and adding a modifier to obtain the thick film resistor paste for the ceramic piezoresistive pressure sensor, wherein the mass ratio of the conductive phase to the inorganic bonding phase to the organic carrier to the modifier is as follows: 50:35:25:4.
Example 3: a preparation method of thick film resistor slurry for a ceramic piezoresistive pressure sensor comprises the following preparation steps:
s1: preparing a conductive phase:
s1.1: adding deionized water into 3.9g of ruthenium trichloride to prepare a 0.15mol/L ruthenium trichloride solution, then adding 1.36g of carbon nano tube, heating to 70 ℃, stirring, then dropwise adding a sodium hydroxide solution, continuously stirring and aging for 4 hours, then centrifugally washing, and calcining for 15 hours at 350 ℃ to obtain a ruthenium oxide/carbon nano tube composite material;
s1.2: mixing 21.3g of ruthenium oxide powder and 4.3g of ruthenium oxide/carbon nanotube composite material to prepare a conductive phase;
s2: preparation of inorganic binder phase: CaO, B2O3、SiO2And ZrO2Adding the mixture into an agate ball-milling tank according to the ratio of 4.5:4:4.5:1.8, stirring for 1.5h, then placing the mixture into a crucible, smelting for 1.7h at 1200 ℃, performing water quenching, and then performing ball milling for 13h to prepare an inorganic bonding phase;
s3: preparation of organic vehicle: mixing diethylene glycol monomethyl ether, tributyl phosphate and ethyl cellulose in a water bath at 70 ℃, stirring until the ethyl cellulose is completely dissolved in a mixed solvent of the diethylene glycol monomethyl ether and the tributyl phosphate, then adding lecithin, cetyl alcohol and 1, 4-butyrolactone, and uniformly stirring to obtain an organic carrier, wherein the mass ratio of the diethylene glycol monomethyl ether to the tributyl phosphate to the ethyl cellulose to the lecithin to the cetyl alcohol to the 1, 4-butyrolactone is 52:40:2:0.5:1.5: 1;
s4: preparing a modifier:
s4.1: putting 0.43g of silicon dioxide particles into 20mL of absolute ethyl alcohol, adding 0.1mL of 3-aminopropyltriethoxysilane, reacting for 7h at 50 ℃, and centrifugally drying to obtain amino modified silicon dioxide particles; dispersing amino modified silica particles into 20mL of toluene, adding 1.2mL of triethylamine, stirring at 0 ℃ for 1h under the protection of nitrogen, adding 1.8mL of 2-bromoisobutyryl bromide, stirring for reacting for 15h, and centrifugally drying to obtain bromine modified silica particles; subsequently, 0.4g of bromine-modified silica particles, 0.025g of ferric trichloride hexahydrate and 0.25g of triphenylphosphine were dispersed in 50ml of N, N-dimethylformamide, and after replacement by argon, 0.12g of ethyl 2-bromoisobutyrate and 40g of methyl methacrylate were added, and mixed with stirring, 0.15g of ascorbic acid was slowly added, reacted at 80 ℃ for 20 hours, washed and dried by centrifugation, to obtain a polyacrylic resin-coated silica; s4.2: mixing polyacrylic resin coated silicon dioxide and lead oxide to obtain a modifier, wherein the polyacrylic resin coated silicon dioxide comprises 70 parts of polyacrylic resin coated silicon dioxide and 35 parts of lead oxide;
s5: mixing and grinding the conductive phase and the inorganic bonding phase, then placing the mixture in an organic carrier, and adding a modifier to obtain the thick film resistor paste for the ceramic piezoresistive pressure sensor, wherein the mass ratio of the conductive phase to the inorganic bonding phase to the organic carrier to the modifier is as follows: 60:40:35:5.
Comparative example 1: the difference from example 1 is that only ruthenium oxide powder was used for the conductive phase.
Comparative example 2: the difference from example 1 is that the same ratio of ruthenium oxide powder and carbon nanotubes were mixed in the preparation of the conductive phase.
Comparative example 3: the difference from example 1 is that no modifier is added to the thick film resistor paste.
Comparative example 4: the difference from example 1 is that the same ratio of silica and lead oxide without polyacrylic resin coating is used in the preparation of the modifier.
Comparative example 5: the difference from example 1 is that the modifier is only polyacrylic acid resin coated silica, and lead oxide is not used.
The thick film resistor pastes prepared in the examples and the comparative examples were fired to obtain thick film resistors with dimensions of 4mm × 4mm, and resistance R and strain coefficient GF of the resistors were tested, wherein the thick film resistor pastes of example 1, comparative example 2 and comparative example 4 were fired by the same process for five groups respectively to test the stability, and the results are shown in the following table.
As can be seen from the above table, comparing example 1 with comparative example 1, comparative example 1 using only ruthenium oxide powder as a conductive phase has a significantly higher resistance than example 1, because the conductive phase prepared by mixing ruthenium oxide powder with a ruthenium oxide/carbon nanotube composite has better properties.
Comparing example 1 with comparative example 2, it can be seen that the thick film resistor paste prepared in example 1 has better measured performance stability after firing, because the ruthenium oxide powder and the carbon nanotubes are mixed to easily cause the agglomeration of the carbon nanotubes, which results in unstable performance, and the ruthenium oxide powder and the ruthenium oxide/carbon nanotube composite material can prevent the agglomeration and have more stable performance.
Comparing example 1 with comparative example 3, it is understood that the strain coefficient greatly increases after the modifier is added, and although the resistance value also increases after the modifier is added, the increase is not so large.
Comparing example 1 with comparative example 4, it can be seen that the thick film resistor paste prepared in example 1 has more stable performance, because the silicon dioxide is coated with polymethacrylic resin, and the dispersibility is better and the agglomeration phenomenon is less.
Comparing example 1 with comparative example 5, it can be seen that the use of lead oxide as a modifier greatly increases the resistance of the thick film resistor paste produced because lead oxide reacts with ruthenium dioxide to produce the ruthenate Pb2Ru2O6.5Which isThe conductive phase is used for relieving the phenomenon that the sheet resistance is suddenly increased due to the fact that the polyacrylic resin coats the silicon dioxide.
Claims (8)
1. A thick film resistor paste for a ceramic piezoresistive pressure sensor, comprising: the components and the parts by mass are 50-60 parts of ruthenium oxide and 5-10 parts of ruthenium oxide/carbon nano tube composite material; inorganic binder phase: the components and the parts by mass are that CaO40-50 parts and B2O340-50 parts of SiO245-55 parts and ZrO215-20 parts of a solvent; organic carrier: the components and the parts by mass are 90-95 parts of organic solvent, 2-5 parts of thickening agent, 0.5-1 part of surfactant, 1-2 parts of thixotropic agent and 0.5-1 part of rheological agent; and a modifier: the components and the parts by mass are 70-90 parts of polyacrylic resin coated silicon dioxide and 30-40 parts of lead oxide.
2. The thick-film resistor paste according to claim 1, wherein the organic solvent is one or a combination of diethylene glycol monomethyl ether, tributyl citrate, tributyl phosphate, terpineol, and butyl carbitol, the thickener is one of ethyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose, the surfactant is lecithin, the thixotropic agent is one or a combination of cetyl alcohol, polyamide wax, and castor oil, and the rheological agent is 1, 4-butyrolactone.
3. The method for preparing a thick film resistor paste for a ceramic piezoresistive pressure sensor according to claim 1, comprising the following steps:
s1: preparing a conductive phase:
s1.1: adding deionized water into ruthenium trichloride to prepare a ruthenium trichloride solution of 0.1-0.15mol/L, then adding a carbon nano tube, heating to 60-70 ℃, stirring, then dropwise adding a sodium hydroxide solution, continuously stirring and aging for 2-4h, then centrifugally washing, and calcining to obtain a ruthenium oxide/carbon nano tube composite material;
s1.2: mixing ruthenium oxide powder and a ruthenium oxide/carbon nano tube composite material to prepare a conductive phase;
s2: preparation of inorganic binder phase: CaO, B2O3、SiO2And ZrO2Adding the mixture into an agate ball-milling tank according to the proportion, stirring for 1-2h, then placing the mixture into a crucible, smelting for 1.5-2h at the temperature of 1100-1300 ℃, and performing ball milling for 10-15h after water quenching to prepare an inorganic bonding phase;
s3: preparation of organic vehicle: mixing an organic solvent and a thickening agent in a water bath at 70-85 ℃, stirring until the thickening agent is completely dissolved in the organic solvent, then adding a surfactant, a thixotropic agent and a rheological agent, and uniformly stirring to obtain an organic carrier;
s4: preparing a modifier:
s4.1: placing the silicon dioxide particles in absolute ethyl alcohol, adding 3-aminopropyltriethoxysilane, reacting for 7-14h at 30-50 ℃, and centrifugally drying to obtain amino modified silicon dioxide particles; dispersing amino modified silica particles into toluene, adding triethylamine, stirring for 1-2h at 0 ℃ under the protection of nitrogen, adding 2-bromine isobutyryl bromide, stirring for reaction for 10-15h, and centrifugally drying to obtain bromine modified silica particles; then, dispersing bromine-modified silica particles, ferric trichloride hexahydrate and triphenylphosphine in N, N-dimethylformamide, replacing by argon, adding ethyl 2-bromoisobutyrate and methyl methacrylate, stirring and mixing, slowly adding ascorbic acid, reacting at 50-80 ℃ for 20-28h, centrifuging, washing and drying to obtain polyacrylic resin coated silica;
s4.2: mixing polyacrylic resin coated silicon dioxide and lead oxide to obtain a modifier;
s5: and mixing and grinding the conductive phase and the inorganic bonding phase, then placing the mixture in an organic carrier, and adding a modifier to obtain the thick-film resistor paste for the ceramic piezoresistive pressure sensor.
4. The method for preparing the thick film resistor paste for the ceramic piezoresistive pressure sensor according to claim 3, wherein the mass ratio of the ruthenium trichloride to the carbon nanotubes in step S1.1 is as follows: 1-3:1.
5. The method as claimed in claim 3, wherein the calcination step S1.1 is carried out at a temperature of 250-350 ℃ for 15-24 h.
6. The method for preparing the thick film resistor paste for the ceramic piezoresistive pressure sensor according to claim 3, wherein the mass ratio of ferric trichloride hexahydrate to triphenylphosphine in step S4.1 is 1: 10-15.
7. The method as claimed in claim 3, wherein the mass ratio of the silica particles modified with bromine to the methyl methacrylate in step S4.1 is 1: 100-150.
8. The method for preparing thick film resistor paste for ceramic piezoresistive pressure sensors according to claim 3, wherein the particle size of the polyacrylic resin coated silica and lead oxide in step S4.2 is 1-3 μm.
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